CN111020696B - Preparation method of efficient crucible with silicon particles as nucleation source - Google Patents
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Abstract
The invention provides a crucible preparation method using silicon particles as a nucleation source, which is characterized by comprising the following steps: s1: preparing a high-purity quartz sand coating on the surface of a crucible, wherein SO is contained in the high-purity quartz sand2The mass fraction is more than or equal to 99.999 percent; s2: preparing a silicon nitride coating on the surface of the high-purity quartz sand coating; s3: preparing a ceramic glue coating on the surface of the silicon nitride coating; s4: and preparing a silicon particle coating on the surface of the ceramic adhesive coating. According to the invention, high-purity silicon particles are used as a nucleation source, a homogeneous nucleation mode is adopted in the ingot casting process to prepare the fully-melted high-efficiency polycrystalline silicon wafer, the technical requirements of spraying and ingot casting processes are greatly reduced, the high-efficiency silicon ingot with uniform and fine crystal patterns is obtained, and the problems of uneven grain size distribution and high dislocation density are avoided.
Description
Technical Field
The invention belongs to the technical field of preparation of crucibles for polycrystalline silicon ingot casting, and particularly relates to a preparation method of a high-efficiency crucible with silicon particles as nucleation sources.
Background
At present, the preparation method of the polycrystalline silicon ingot is mainly prepared by utilizing a directional solidification system provided by GT Solar, and generally comprises the steps of heating, melting, crystal growth, annealing, cooling and the like. In the process of solidification and crystal growth, the top temperature and the opening degree of the side heat-insulating cover are controlled, so that the molten silicon liquid obtains enough supercooling degree solidification crystals at the bottom of the crucible. An important auxiliary material used in the process of polycrystal ingot casting, namely a quartz crucible for polycrystal ingot casting, has the advantages that the bottom of a common crucible is isotropic, the nucleation of silicon liquid in the initial crystallization stage can not be effectively controlled, the problems of uneven grain size distribution (from dozens of microns to tens of centimeters) and high dislocation density exist, the improvement of the conversion efficiency of a polycrystalline silicon wafer is greatly influenced, and the requirement of an ingot casting plant for developing a high-efficiency ingot casting technology is more and more difficult to meet.
Aiming at the problems that the bottom of a crucible for common crucible ingot casting is not isotropic, the initial stage of the ingot casting is random spontaneous nucleation, the dislocation density of a silicon ingot is high, the photoelectric conversion efficiency is low and the like, in the prior art, a method such as preparing a groove with a certain size or a uniform salient point at the bottom of the crucible is adopted to form anisotropic structural characteristics at the bottom of the crucible, so that the optimal nucleation can be selected during the initial stage of the ingot casting so as to achieve the purpose of improving the photoelectric conversion efficiency; although the method accords with the nucleation requirement in principle, the artificially manufactured grooves or salient points have relatively large size and are heterogeneous nucleation, the driving force required in the initial stage of nucleation is large, and the driving force (or called supercooling degree) required by the nucleation is difficult to achieve by a common cast ingot, so that the scheme is only limited to laboratory research and effective mass production cannot be obtained; based on the principle, researchers also put forward that quartz sand with certain granularity is paved at the bottom of a crucible to replace grooves or salient points and the like, and pores formed among the quartz sand are utilized to enable the bottom of the crucible to have the characteristic of anisotropy, so that the purpose of controlling nucleation and improving the photoelectric conversion efficiency of a silicon ingot is achieved, the method is simple in manufacturing process and obviously helps to control nucleation, the photoelectric conversion efficiency of the silicon wafer can be greatly improved from 16.8% -17.0% of a common ingot to 17.6% -17.7%, and the silicon wafer is paid attention and popularized to the market, but the following problems exist at the same time: firstly, the nucleation source layer laid at the bottom of the high-efficiency crucible in the current market is generally high-purity quartz sand, but the adopted heterogeneous nucleation mode has higher requirements on the spraying process and the nucleation energy, and the process popularization technology has higher threshold and is not beneficial to popularization; secondly, at present, because the conventionally used high-efficiency crucible is generally formed by directly spraying a layer of high-purity silicon nitride on high-purity quartz sand paved at the bottom of the crucible, crystal growth is normally carried out, but heterogeneous nucleation is carried out in the process, and the driving force required by nucleation is obviously increased compared with homogeneous nucleation, so that a common efficiency silicon wafer with 15% -20% of photoelectric conversion efficiency of 16.8% -17.0% is generally generated when a common high-efficiency crucible is used for ingot casting, the output of the high-efficiency silicon wafer is greatly influenced, and the photovoltaic power generation cost is increased. Therefore, the selection of a crucible preparation method with simple preparation process and low cost to overcome the problems of uneven grain size distribution and high dislocation density at the initial stage of crystallization is an urgent technical problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a high-efficiency crucible taking silicon particles as a nucleation source, which comprises the following steps:
s1: preparing a high-purity quartz sand coating on the surface of a crucible, wherein SiO in the high-purity quartz sand2The mass fraction is more than or equal to 99.999 percent;
s2: preparing a silicon nitride coating on the surface of the high-purity quartz sand coating;
s3: preparing a ceramic glue coating on the surface of the silicon nitride coating;
s4: and preparing a silicon particle coating on the surface of the ceramic adhesive coating.
Further, the step S1 includes:
s11: single crystal high purity quartz sand: melting high-purity quartz sand: adding water into a ball mill according to the mass ratio of 1 (1-2) to 1-3, taking metal oxide as a grinding ball material, and carrying out ball milling for 16-20 h to prepare the product with the particle size D50The quartz sand slurry is 6-8 mu m quartz sand slurry, and the metal impurity content of the quartz sand slurry is less than or equal to 10 ppm; preferably, the single crystal high purity quartz sand: melting high-purity quartz sand: the mass ratio of water is 1:1.5: 2; the granularity of the single crystal high-purity quartz sand and the granularity of the fused high-purity quartz sand are both 50-200 meshes, and further preferably, the granularity of the single crystal high-purity quartz sand and the granularity of the fused high-purity quartz sand are both 100 meshes; the metal oxide is zirconium oxide; the ball milling time is 18 h; the particle diameter D of the quartz sand slurry50Is 7 μm;
s12: mixing the quartz sand slurry obtained in the step S11 with alcohol-based silica sol according to the mass ratio of 10: 2-4, mixing, stirring and homogenizing for 6-8 hours to form homogenized quartz mortar material, wherein the content of metal impurities in the homogenized quartz mortar material is less than or equal to 10 ppm; preferably, the mass ratio of the quartz sand slurry to the silica sol is 10: 3; the homogenization time is 7 h; preferably, the alcohol-based silica sol contains nano SiO2The mass fraction of the particles is 20%, the mass fraction of the ethanol is 65%, the mass fraction of the pure water is 15%, and the content of metal impurities is less than or equal to 1 ppm;
s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the mass of the homogenized quartz sand slurry for brushing each crucible is 600-1200 g; preferably, the mass of the homogenized quartz sand slurry for each crucible is 900g by brushing;
wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
further, the step of S2 includes:
s21: uniformly mixing silicon nitride, ceramic glue and pure water in a mass ratio of 1 (1-2) to 1 to obtain a silicon nitride mixed solution; preferably, the silicon nitride particle diameter D502.1-2.3 μm, total metal impurity content less than or equal to 5ppm, and beta phase mass percentage content of 50% -60%; preferably, the ceramic glue is a polyvinyl alcohol aqueous solution with the mass fraction of 3-8% and the polymerization degree of more than or equal to 8000, and further preferably, the ceramic glue is a polyvinyl alcohol aqueous solution with the mass fraction of 5% and the polymerization degree of more than or equal to 8000; preferably, the mass ratio of the silicon nitride to the ceramic adhesive to the pure water is 1:1.5: 1; more preferably, the silicon nitride particle diameter D502.2 mu m, the content of total metal impurities is less than or equal to 5ppm, and the mass percentage content of beta phase is 55 percent;
s22: coating the silicon nitride mixed solution on the surface of the high-purity quartz sand coating obtained in S13, and standing for 6-8 hours at room temperature to obtain a silicon nitride coating; preferably, the mass of the silicon nitride mixed liquor for brushing each crucible is 100-150 g, and further preferably, the mass of the silicon nitride mixed liquor for brushing each crucible is 130 g;
further, the step S3 includes: brushing a ceramic glue solution on the surface of the silicon nitride coating to form a ceramic glue layer, wherein the mass of the ceramic glue solution for brushing each crucible is 300-400 g, and preferably, the mass of the ceramic glue solution for brushing each crucible is 350 g; preferably, the ceramic glue is a polyvinyl alcohol aqueous solution with the mass fraction of 3-8% and the polymerization degree of more than or equal to 8000, and further preferably, the ceramic glue is a polyvinyl alcohol aqueous solution with the mass fraction of 5% and the polymerization degree of more than or equal to 8000;
further, the step S4 includes: uniformly spraying a layer of silicon particles with the granularity of 30-80 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and then drying the crucible for 40-60 min at 80-100 ℃ to form a silicon particle layer; preferably, the particle size of the silicon particles is 60 meshes; the spraying mode is an electrostatic spraying mode; the mass of the silicon particles for each crucible is 150-180 g; the drying temperature is 90 ℃ and the drying time is 50 min.
Advantageous effects
The invention has the following beneficial effects:
1. the method for preparing the high-purity quartz sand coating by mixing the single-crystal high-purity quartz sand with the fused high-purity quartz sand and then mixing the mixture with the alcohol-based silica sol has the following advantages: (1) compared with polycrystalline high-purity quartz sand, the single-crystal high-purity quartz sand has the advantages that part of the single-crystal high-purity quartz sand is higher in purity, volume change caused by phase change of the single-crystal quartz sand at high temperature is large, compactness of a high-purity quartz sand coating is improved by adjusting the proportion range, and the impurity isolation effect is better achieved; (2) the colloidal alcohol system silica sol formed by the silicon dioxide nano particles, ethanol and pure water is adopted to prepare the high-purity quartz coating, on one hand, the viscosity of slurry can be greatly reduced, and the brushing performance can be improved, on the other hand, the volatile solvent ethanol is contained, the drying performance of the coating is greatly improved, meanwhile, the damage to the surface structure of the high-purity quartz coating caused by multiple brushing is reduced, the compactness of the high-purity quartz coating is enhanced, and impurities are better blocked. The two are combined, so that impurity diffusion of the crucible to the silicon ingot is effectively reduced, and the width of a red zone at the bottom is reduced by more than 10 mm.
2. The silicon nitride coating is prepared by adopting the silicon nitride, the ceramic adhesive and the water in a certain ratio, so that the operation of heating and drying is avoided, the silicon nitride coating at low temperature has better strength and water resistance, and the coating is prevented from being damaged when the silicon nitride adhesive coating is brushed at a later stage. The prepared silicon nitride coating has stronger compactness and more stability.
3. The high-purity silicon particles are used as nucleation sources, and the fully-melted high-efficiency polycrystalline silicon wafer is prepared in a homogeneous nucleation mode in the ingot casting process, so that the technical requirements of spraying and ingot casting processes are greatly reduced, the high-efficiency silicon ingot with uniform and fine crystal patterns is obtained, and the problems of uneven grain size distribution and high dislocation density are solved.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby. It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which the invention pertains.
Example 1:
a preparation method of a high-efficiency crucible with silicon particles as a nucleation source comprises the following steps:
s11: monocrystalline high-purity quartz sand with the granularity of 50 meshes is prepared by the following steps: melting high-purity quartz sand and water in a mass ratio of 1000 g: 1000 g: adding 1000g of the mixture into a ball mill, taking zirconia as a grinding ball material, and carrying out ball milling for 16h to prepare the mixture into a particle size D50Is quartz mortar with the particle size of 8 mu m, and the metal impurity content of the quartz mortar is less than or equal to 10 ppm; s12: mixing the quartz sand slurry obtained in S11 with nano SiO2Mixing, stirring and homogenizing 20% of particle mass fraction, 65% of ethanol mass fraction and 15% of pure water mass fraction for 6 hours to form homogenized quartz sand slurry, wherein the mass ratio of the alcohol-based silica sol containing metal impurities is less than or equal to 1ppm, and the metal impurity content of the homogenized quartz sand slurry is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the amount of the homogenized quartz sand slurry brushed on the crucible is 600 g; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s21: silicon nitride (particle diameter D)502.1 mu m, less than or equal to 5ppm of total metal impurities and 50 percent of beta phase by mass percent, ceramic glue (polyvinyl alcohol aqueous solution with 3 percent of mass fraction and more than or equal to 8000 percent of polymerization degree), and pure water in a mass ratio of 500g: 500g: 500g of the mixture is uniformly mixed to obtain a silicon nitride mixed solution; s22: coating the silicon nitride mixed solution on the surface of the high-purity quartz sand coating obtained in S13, standing for 6 hours at room temperature to obtain a silicon nitride coating, wherein the weight of the silicon nitride mixed solution used in the coating is 100g per crucible;
s3: coating ceramic glue (a polyvinyl alcohol aqueous solution with the mass fraction of 3%) on the surface of the silicon nitride coating to form a ceramic glue layer, wherein the ceramic glue used for coating is 300g per crucible;
s4: uniformly and electrostatically spraying a layer of silicon particles with the particle size of 30 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and then drying the crucible at 80 ℃ for 60min to form a silicon particle layer; the amount of the silicon particles used per crucible was 150 g. The photoelectric conversion efficiency of the prepared silicon wafer is 18.5%.
Example 2:
a preparation method of a high-efficiency crucible with silicon particles as a nucleation source comprises the following steps:
s11: single crystal high-purity quartz sand with the granularity of 200 meshes is prepared by the following steps: melting high-purity quartz sand and water in a mass ratio of 1000 g: 2000 g: adding 3000g of the mixture into a ball mill, taking zirconia as a grinding ball material, and carrying out ball milling for 20 hours to prepare the mixture into a particle size D50Is quartz mortar with the particle size of 6 mu m, and the metal impurity content of the quartz mortar is less than or equal to 10 ppm; s12: mixing the quartz sand slurry obtained in S11 with nano SiO2Mixing alcohol-based silica sol with the mass fraction of 20% of particles, the mass fraction of ethanol of 65% and the mass fraction of pure water of 15% and the mass ratio of metal impurities of less than or equal to 1ppm, stirring and homogenizing for 8 hours to form homogenized quartz sand slurry, wherein the content of the metal impurities of the homogenized quartz sand slurry is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the amount of the homogenized quartz sand slurry brushed on the crucible is 1200g per crucible; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s21: silicon nitride (particle diameter D)502.3 mu m, the content of total metal impurities is less than or equal to 5ppm, the mass percentage of beta phase is 60 percent), ceramic glue (polyvinyl alcohol aqueous solution with mass fraction of 8 percent and polymerization degree of more than or equal to 8000), pure water in a mass ratio of 500g: 1000 g: 500g of the mixture is uniformly mixed to obtain a silicon nitride mixed solution; s22: coating the silicon nitride mixed solution on the surface of the high-purity quartz sand coating obtained in S13, and standing for 8 hours at room temperature to obtain a silicon nitride coating, wherein the weight of the silicon nitride mixed solution used in the coating is 150g per crucible;
s3: coating ceramic glue (aqueous solution of polyvinyl alcohol with the mass fraction of 8%) on the surface of the silicon nitride coating to form a ceramic glue layer, wherein the ceramic glue used for coating is 400g for each crucible;
s4: uniformly and electrostatically spraying a layer of silicon particles with the particle size of 80 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and then drying the crucible at 100 ℃ for 40min to form a silicon particle layer; the amount of the silicon particles used was 180g per crucible. The photoelectric conversion efficiency of the prepared silicon wafer is 19.0%.
Example 3:
a preparation method of a high-efficiency crucible with silicon particles as a nucleation source comprises the following steps:
s11: monocrystalline high-purity quartz sand with the granularity of 100 meshes is prepared by the following steps: melting high-purity quartz sand and water in a mass ratio of 1000 g: 1500g of: adding the mixture into a ball mill according to the proportion of 2000g, taking zirconia as a grinding ball material, and carrying out ball milling for 18h to prepare the material with the particle size D50Is 7 mu m of quartz mortar, and the metal impurity content of the quartz mortar is less than or equal to 10 ppm; s12: mixing the quartz sand slurry obtained in S11 with nano SiO2Mixing, stirring and homogenizing 20% of particle mass fraction, 65% of ethanol mass fraction and 15% of pure water mass fraction, wherein the mass ratio of the alcohol-based silica sol containing metal impurities is less than or equal to 1ppm is 4500g:1350g, and then forming homogenized quartz sand slurry, and the content of the metal impurities in the homogenized quartz sand slurry is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the amount of the homogenized quartz sand slurry brushed on the crucible is 900g per crucible; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s21: silicon nitride (particle diameter D)502.2 mu m, the content of total metal impurities is less than or equal to 5ppm, the mass percentage of beta phase is 55 percent), ceramic glue (polyvinyl alcohol aqueous solution with the mass fraction of 5 percent and the polymerization degree of more than or equal to 8000), pure water and the balance of the weight ratio of 500g: 750 g: 500g of the mixture is uniformly mixed to obtain a silicon nitride mixed solution; s22: coating the silicon nitride mixed solution on the surface of the high-purity quartz sand coating obtained in S13, standing for 7 hours at room temperature to obtain a silicon nitride coating, and coating the silicon nitride coatingThe weight of the silicon nitride mixed liquid is 130g of each crucible;
s3: coating ceramic glue (a polyvinyl alcohol aqueous solution with the mass fraction of 5%) on the surface of the silicon nitride coating to form a ceramic glue layer, wherein the ceramic glue used for coating is 350g for each crucible;
s4: uniformly and electrostatically spraying a layer of silicon particles with the particle size of 60 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and then drying the crucible at 90 ℃ for 50min to form a silicon particle layer; the amount of the silicon particles used per crucible was 165 g. The photoelectric conversion efficiency of the prepared silicon wafer is 19.8%.
Comparative example 1:
a preparation method of a high-efficiency crucible with silicon particles as a nucleation source comprises the following steps:
s11: melting high-purity quartz sand with the granularity of 100 meshes: the mass ratio of water is 2500 g: adding the mixture into a ball mill according to the proportion of 2000g, taking zirconia as a grinding ball material, and carrying out ball milling for 18h to prepare the material with the particle size D50Is 7 mu m of quartz mortar, and the metal impurity content of the quartz mortar is less than or equal to 10 ppm; s12: mixing the quartz sand slurry obtained in S11 with nano SiO2Mixing, stirring and homogenizing 20% of particle mass fraction, 65% of ethanol mass fraction and 15% of pure water mass fraction, wherein the mass ratio of the alcohol-based silica sol containing metal impurities is less than or equal to 1ppm is 4500g:1350g, and then forming homogenized quartz sand slurry, and the content of the metal impurities in the homogenized quartz sand slurry is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the amount of the homogenized quartz sand slurry brushed on the crucible is 900g per crucible; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s21: silicon nitride (particle diameter D)502.2 mu m, the content of total metal impurities is less than or equal to 5ppm, the mass percentage of beta phase is 55 percent), ceramic glue (polyvinyl alcohol aqueous solution with the mass fraction of 5 percent and the polymerization degree of more than or equal to 8000), pure water and the balance of the weight ratio of 500g: 750 g: 500g of the mixture is uniformly mixed to obtain a silicon nitride mixed solution; s22: coating the silicon nitride mixed solution on the high-purity quartz sand obtained by S13Standing for 7 hours at room temperature to obtain a silicon nitride coating, wherein the weight of the silicon nitride mixed solution used for brushing is 130g of that of each crucible;
s3: coating ceramic glue (a polyvinyl alcohol aqueous solution with the mass fraction of 5%) on the surface of the silicon nitride coating to form a ceramic glue layer, wherein the ceramic glue used for coating is 350g for each crucible;
s4: uniformly and electrostatically spraying a layer of silicon particles with the particle size of 60 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and then drying the crucible at 90 ℃ for 50min to form a silicon particle layer; the amount of silicon particles used per crucible was 165 g. The photoelectric conversion efficiency of the prepared silicon wafer is 17.5%.
Comparative example 2:
a preparation method of a high-efficiency crucible with silicon particles as a nucleation source comprises the following steps:
s11: monocrystalline high-purity quartz sand with the granularity of 100 meshes is prepared by the following steps: melting high-purity quartz sand: the mass ratio of water is 1000 g: 1500g of: adding 2000g of the mixture into a ball mill, taking zirconium oxide as a grinding ball material, and carrying out ball milling for 18h to prepare quartz mortar with the particle size D50 of 7 mu m, wherein the content of metal impurities in the quartz mortar is less than or equal to 10 ppm; s12: mixing the quartz sand slurry obtained in the step S11 with common silica sol in a mass ratio of 4500g:1350g, stirring and homogenizing for 8 hours to form homogenized quartz sand slurry, wherein the content of metal impurities in the homogenized quartz sand slurry is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the amount of the homogenized quartz sand slurry brushed on the crucible is 900g per crucible; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s21: silicon nitride (particle diameter D)502.2 mu m, the content of total metal impurities is less than or equal to 5ppm, and the mass percentage content of beta phase is 55 percent), common silica sol and pure water in a mass ratio of 500g: 750 g: 500g of the mixture is uniformly mixed to obtain a silicon nitride mixed solution; s22: coating the silicon nitride mixed solution on the surface of the high-purity quartz sand coating obtained in S13, standing for 7 hours at room temperature to obtain a silicon nitride coating, andthe weight of the silicon nitride mixed solution used for brushing is 130g of each crucible;
s3: coating ceramic glue (5 mass percent of polyvinyl alcohol aqueous solution with the polymerization degree being more than or equal to 8000) on the surface of the silicon nitride coating to form a ceramic glue layer, wherein the ceramic glue used in the coating is 350 g/piece;
s4: uniformly and electrostatically spraying a layer of silicon particles with the particle size of 60 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and then drying the crucible at 90 ℃ for 50min to form a silicon particle layer; the amount of silicon particles used per crucible was 165 g. The photoelectric conversion efficiency of the prepared silicon wafer is 17.3%.
Comparative example 3:
a preparation method of a high-efficiency crucible with silicon particles as a nucleation source comprises the following steps:
s11: monocrystalline high-purity quartz sand with the granularity of 100 meshes is prepared by the following steps: melting high-purity quartz sand and water in a mass ratio of 1000 g: 1500g of: adding the mixture into a ball mill according to the proportion of 2000g, taking zirconia as a grinding ball material, and carrying out ball milling for 18h to prepare the material with the particle size D50Is 7 mu m of quartz mortar, and the metal impurity content of the quartz mortar is less than or equal to 10 ppm; s12: mixing the quartz sand slurry obtained in S11 with nano SiO2Mixing, stirring and homogenizing 20% of particle mass fraction, 65% of ethanol mass fraction and 15% of pure water mass fraction, wherein the mass ratio of the alcohol-based silica sol containing metal impurities is less than or equal to 1ppm is 4500g:1350g, and then forming homogenized quartz sand slurry, and the content of the metal impurities in the homogenized quartz sand slurry is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the amount of the homogenized quartz sand slurry brushed on the crucible is 900g per crucible; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s21: silicon nitride (particle diameter D)502.2 mu m, the content of total metal impurities is less than or equal to 5ppm, and the mass percentage content of beta phase is 55 percent), and pure water is mixed according to the mass ratio of 500g: 1250g are mixed evenly to obtain silicon nitride mixed solution; s22: the silicon nitride mixed solution is coated on the surface of the high-purity quartz sand coating obtained in S13,then standing for 7 hours at room temperature to obtain a silicon nitride coating, wherein the weight of the silicon nitride mixed solution used for brushing is 130g of that of each crucible;
s3: coating ceramic glue (a polyvinyl alcohol aqueous solution with the mass fraction of 5% and the polymerization degree of more than or equal to 8000) on the surface of the silicon nitride coating to form a ceramic glue layer, wherein the ceramic glue used in the coating is 350g per crucible;
s4: uniformly and electrostatically spraying a layer of silicon particles with the particle size of 60 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and then drying the crucible at 90 ℃ for 50min to form a silicon particle layer; the amount of the silicon particles used per crucible was 165 g. The photoelectric conversion efficiency of the prepared silicon wafer is 16.9%.
Comparative example 4:
a method of preparing a crucible comprising the steps of:
s11: single crystal high purity quartz sand: melting high-purity quartz sand: the mass ratio of water is 1000 g: 1500g of: adding 2000g of the mixture into a ball mill, taking zirconium oxide as a grinding ball material, and carrying out ball milling for 18h to prepare quartz mortar with the particle size D50 of 7 mu m, wherein the content of metal impurities in the quartz mortar is less than or equal to 10 ppm; s12: mixing, stirring and homogenizing the quartz mortar material obtained in the step S11 and alcoholic silicon sol containing 20 mass percent of nano SiO2 particles, 65 mass percent of ethanol and 15 mass percent of pure water, wherein the mass ratio of the alcoholic silicon sol containing metal impurities is less than or equal to 1ppm is 4500g:1350g to form homogenized quartz mortar material, and the content of the metal impurities in the homogenized quartz mortar material is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the amount of the homogenized quartz sand slurry brushed on the crucible is 900g per crucible; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and SiO in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s21: silicon nitride (particle diameter D)502.2 mu m, less than or equal to 5ppm of total metal impurities, 55 percent of beta phase by mass, ceramic glue (5 percent of polyvinyl alcohol aqueous solution by mass), and pure water in a mass ratio of 500g: 750 g: 500g of the mixture is uniformly mixed to obtain a silicon nitride mixed solution; s22: coating the silicon nitride mixed solutionAnd (4) standing the surface of the high-purity quartz sand coating obtained in the step S13 at room temperature for 7 hours to obtain a silicon nitride coating, wherein the weight of the silicon nitride mixed solution used for brushing is 130g per crucible. The photoelectric conversion efficiency of the prepared silicon wafer is 16.5%.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (6)
1. A preparation method of a high-efficiency crucible taking silicon particles as a nucleation source is characterized by comprising the following steps:
the step of S1 includes: s11: single crystal high purity quartz sand: melting high-purity quartz sand: adding water into a ball mill according to the mass ratio of 1 (1-2) to 1-3, taking metal oxide as a grinding ball material, and carrying out ball milling for 16-20 h to prepare the product with the particle size D50The quartz sand slurry is 6-8 mu m quartz sand slurry, and the metal impurity content of the quartz sand slurry is less than or equal to 10 ppm; s12: mixing the quartz sand slurry obtained in the step S11 with alcohol-based silica sol in a mass ratio of 10: 2-4, stirring and homogenizing for 6-8 hours to form homogenized quartz sand slurry, wherein the content of metal impurities in the homogenized quartz sand slurry is less than or equal to 10 ppm; s13: brushing the homogenized quartz sand slurry on the inner surface of the crucible to form a high-purity quartz sand coating, wherein the mass of the homogenized quartz sand slurry for brushing each crucible is 600-1200 g; wherein the single crystal high-purity quartz sand, the fused high-purity quartz sand and Si O in the high-purity quartz sand2The mass fractions are all more than or equal to 99.999 percent;
s2: preparing a silicon nitride coating on the surface of the high-purity quartz sand coating, which specifically comprises the following steps: s21: uniformly mixing silicon nitride, ceramic glue and pure water in a mass ratio of 1 (1-2) to 1 to obtain a silicon nitride mixed solution; s22: coating the silicon nitride mixed solution on the surface of the high-purity quartz sand coating obtained in S13, and standing for 6-8 hours at room temperature to obtain a silicon nitride coating;
s3: preparing a ceramic adhesive coating on the surface of the silicon nitride coating, wherein the mass of the ceramic adhesive solution for brushing each crucible is 300-400 g;
s4: preparing a silicon particle coating on the surface of the ceramic adhesive coating, which specifically comprises the following steps: and uniformly spraying a layer of silicon particles with the granularity of 30-80 meshes and the purity of 99.999% on the surface of the ceramic glue layer, and drying the crucible for 40-60 min at 80-100 ℃ to form a silicon particle layer.
2. The method for preparing a high-efficiency crucible using silicon particles as a nucleation source according to claim 1, wherein in step S1, the single-crystal high-purity quartz sand and the fused high-purity quartz sand each have a particle size of 50 to 200 meshes.
3. The method for preparing a high-efficiency crucible using silicon particles as a nucleation source as claimed in claim 1, wherein in step S2, the silicon nitride particle diameter D is502.1-2.3 μm, total metal impurity content less than or equal to 5ppm, and beta phase mass percentage content of 50-60%.
4. The method for preparing a high-efficiency crucible using silicon particles as a nucleation source according to claim 1, wherein in step S2, the mass of the silicon nitride mixed solution for each crucible is 100-150 g.
5. The method for preparing a high-efficiency crucible using silicon particles as a nucleation source as claimed in claim 1, wherein in steps S2 and S3, the ceramic glue is an aqueous solution of polyvinyl alcohol with a mass fraction of 3-8% and a degree of polymerization of more than or equal to 8000.
6. The method for preparing the high-efficiency crucible by using the silicon particles as the nucleation source according to claim 5, wherein the amount of the silicon particles is 150-180 g per crucible.
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